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  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
  • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
  • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
  • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
  • C07C2/08—Catalytic processes
  • C07C2/26—Catalytic processes with hydrides or organic compounds
  • C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
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  • C08F4/00—Polymerisation catalysts
  • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
  • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
  • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
  • C08F4/70—Iron group metals, platinum group metals or compounds thereof
  • C08F4/7001—Iron group metals, platinum group metals or compounds thereof the metallic compound containing a multidentate ligand, i.e. a ligand capable of donating two or more pairs of electrons to form a coordinate or ionic bond
  • C08F4/7039—Tridentate ligand
  • C08F4/704—Neutral ligand
  • C08F4/7042—NNN
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  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
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  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
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  • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
  • B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
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  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
  • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
  • B01J31/146—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of boron
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  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
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  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/22—Organic complexes
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  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F10/02—Ethene
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  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
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  • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
  • B01J2231/20—Olefin oligomerisation or telomerisation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/001—General concepts, e.g. reviews, relating to catalyst systems and methods of making them, the concept being defined by a common material or method/theory
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  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/001—General concepts, e.g. reviews, relating to catalyst systems and methods of making them, the concept being defined by a common material or method/theory
  • B01J2531/002—Materials
  • B01J2531/005—Catalytic metals
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  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
  • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
  • B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
  • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
  • B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
  • B01J2531/0244—Pincer-type complexes, i.e. consisting of a tridentate skeleton bound to a metal, e.g. by one to three metal-carbon sigma-bonds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
  • B01J2531/84—Metals of the iron group
  • B01J2531/842—Iron
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
  • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
  • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
  • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F110/02—Ethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
  • C08F2500/02—Low molecular weight, e.g. <100,000 Da.
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  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
  • C08F2500/03—Narrow molecular weight distribution, i.e. Mw/Mn < 3

Definitions

• the present invention relates to a catalyst and a production method of an oligomer, and more particularly, to a method for producing an oligomer from a monomer comprising an olefin, and a catalyst therefor.
• catalysts used in the copolymerization of ethylene and an ⁇ -olefin catalysts consisting of a metallocene compound and methylaluminoxane, palladium-based catalysts, iron complexes and cobalt complexes are known (Non Patent Literatures 1 to 3, Patent Literatures 1 to 3).
• catalysts to produce block copolymers consisting of a metallocene compound, a palladium-based catalyst and dialkyl zinc are known (Non Patent Literature 7, Patent Literature 4).
• the object of the present invention is to provide a production method of an oligomer, and a catalyst therefor, which can produce an oligomer with a high catalyst efficiency in the oligomerization of a polymerizable monomer comprising an olefin.
• the present invention provides a method for producing an oligomer, the method comprising a step of oligomerizing a polymerizable monomer comprising an olefin in the presence of a catalyst comprising an iron complex represented by the following Formula (1) and trialkylaluminum.
• R represents a hydrocarbyl group having 1 to 6 carbon atoms or an aromatic group having 6 to 12 carbon atoms, a plurality of R in the same molecule may be the same or different, R′ represents a free radical having an oxygen atom and/or a nitrogen atom, a plurality of R′ in the same molecule may be the same or different, and Y represents a chlorine atom or a bromine atom.
• an oligomer can be produced with a high catalyst efficiency, by oligomerizing a polymerizable monomer comprising an olefin in the presence of the above specific catalyst.
• the above trialkylaluminum may comprise trimethylaluminum.
• the catalyst may further comprise a boron compound, and may further comprise methylaluminoxane.
• the above catalyst may further comprise a compound represented by the following Formula (2).
• R′′ represents a hydrocarbyl group having 1 to 6 carbon atoms or an aromatic group having 6 to 12 carbon atoms, a plurality of R′′ in the same molecule may be the same or different, R′′′ represents a free radical having an oxygen atom and/or a nitrogen atom, and a plurality of R′′′ in the same molecule may be the same or different.
• the present invention also provides a catalyst comprising an iron complex represented by the following Formula (1) and trialkylaluminum.
• R represents a hydrocarbyl group having 1 to 6 carbon atoms or an aromatic group having 6 to 12 carbon atoms, a plurality of R in the same molecule may be the same or different, R′ represents a free radical having an oxygen atom and/or a nitrogen atom, a plurality of R′ in the same molecule may be the same or different, and Y represents a chlorine atom or a bromine atom.
• Oligomerizing a polymerizable monomer comprising an olefin using the above catalyst allows to produce an oligomer with a high catalyst efficiency.
• the catalyst may further comprise a boron compound, and may further comprise methylaluminoxane.
• the above catalyst may further comprise a compound represented by the following Formula (2).
• R′′ represents a hydrocarbyl group having 1 to 6 carbon atoms or an aromatic group having 6 to 12 carbon atoms, a plurality of R′′ in the same molecule may be the same or different, R′′′ represents a free radical having an oxygen atom and/or a nitrogen atom, and a plurality of R′′′ in the same molecule may be the same or different.
• the present invention can provide a method for producing an oligomer, and a catalyst therefor, which can produce an oligomer with a high catalyst efficiency in the oligomerization of a polymerizable monomer comprising an olefin.
• the production method of the oligomer according to this embodiment includes a step of oligomerizing a polymerizable monomer comprising an olefin in the presence of a catalyst.
• the catalyst for the oligomerization contains an iron complex and trialkylaluminum.
• the iron complex is represented by the following Formula (1).
• R represents a hydrocarbyl group having 1 to 6 carbon atoms or an aromatic group having 6 to 12 carbon atoms, and a plurality of R in the same molecule may be the same or different.
• R′ represents an organic group having an oxygen atom and/or a nitrogen atom, and a plurality of R′ in the same molecule may be the same or different.
• Y represents a chlorine atom or a bromine atom.
• hydrocarbyl groups having 1 to 6 carbon atoms include alkyl groups having 1 to 6 carbon atoms and alkenyl groups having 2 to 6 carbon atoms.
• the hydrocarbyl group may be either linear, branched or cyclic.
• the hydrocarbyl group may also be a monovalent group in which a linear or branched hydrocarbyl group and a cyclic hydrocarbyl group are bonded.
• alkyl groups having 1 to 6 carbon atoms include linear alkyl groups having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a n-propyl group, a n-butyl group, a n-pentyl group and a n-hexyl group; branched alkyl groups having 3 to 6 carbon atoms such as an iso-propyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group, a branched pentyl group (including all structural isomers), and a branched hexyl group (including all structural isomers); and cyclic alkyl groups having 1 to 6 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
• alkenyl groups having 2 to 6 carbon atoms include linear alkenyl groups having 2 to 6 carbon atoms such as an ethenyl group (vinyl group), a n-propenyl group, a n-butenyl group, a n-pentenyl group, and a n-hexenyl group; branched alkenyl groups having 2 to 6 carbon atoms such as an iso-propenyl group, an iso-butenyl group, a sec-butenyl group, a tert-butenyl group, a branched pentenyl group (including all structural isomers), and a branched hexenyl group (including all structural isomers); and cyclic alkenyl groups having 2 to 6 carbon atoms such as a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, a cyclopentadienyl group
• aromatic groups having 6 to 12 carbon atoms include a phenyl group, a toluyl group, a xylyl group and a naphthyl group.
• a plurality of R in the same molecule may be the same or different, but from a viewpoint of simplifying the synthesis of the compound, they may be the same.
• the organic group having an oxygen atom and/or a nitrogen atom may be a free radical having 0 to 6 carbon atoms and having an oxygen atom and/or a nitrogen atom, and examples thereof include a methoxy group, an ethoxy group, an isopropoxy group and a nitro group.
• iron complex examples include the compounds represented by the following Formulas (1a) to (1h). These iron complexes may be used singly or in combinations of two or more.
• the compound constituting the ligand (hereinafter sometimes referred to as a diimine compound) can be synthesized, for example, by dehydration condensation of dibenzoylpyridine and an aniline compound in the presence of an acid.
• a preferable aspect of the production method of the above diimine compound includes a first step in which 2,6-dibenzoylpyridine, an aniline compound and an acid are dissolved in a solvent and are subjected to dehydration condensation under heating the solvent to reflux, and a second step in which the reaction mixture after the first step is subjected to separation/purification treatment to obtain the diimine compound.
• An example of the acid used in the first step is an organic aluminum compound.
• the organic aluminum compounds include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride and methylaluminoxane.
• a protonic acid can also be used as the acid used in the first step.
• the protonic acid is used as a proton-donating acid catalyst.
• the protonic acid used is not particularly limited, but it is preferably an organic acid. Examples of such protonic acid include acetic acid, trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid and paratoluenesulfonic acid. When these protonic acids are used, it is preferable to remove by-product water using a Dean-Stark water separator or the like. Moreover, it is also possible to perform the reaction in the presence of an adsorbent such as molecular sieves.
• the amount of the protonic acid added is not particularly limited, but may be the amount of catalyst.
• examples of the solvent used in the first step include hydrocarbon solvents and alcohol solvents.
• examples of the hydrocarbon solvents include hexane, heptane, octane, benzene, toluene, xylene, cyclohexane and methylcyclohexane.
• examples of the alcohol solvents include methanol, ethanol and isopropyl alcohol.
• reaction conditions of the first step can be appropriately selected according to the kind and amount of the raw material compound, acid and solvent.
• the separation/purification treatment in the second step is not particularly limited, but examples thereof include silica gel column chromatography and recrystallization.
• the above mentioned organic aluminum compound as the acid it is preferable to mix the reaction solution with a basic aqueous solution and separate and remove the aluminum, followed by purification.
• the iron complex in this embodiment contains iron as the central metal.
• the method for mixing the above diimine compound with iron is not particularly limited, but examples thereof include:
• the method for removing the complex from the mixture of the diimine compound and iron is not particularly limited, but examples thereof include:
• a washing treatment with a solvent capable of dissolving the unreacted diimine compound a washing treatment with a solvent capable of dissolving the unreacted iron salt, and a recrystallization treatment using an appropriate solvent or the like may be performed.
• the solvents capable of dissolving the diimine compound include anhydrous ether, tetrahydrofuran, benzene, toluene, xylene, cyclohexane and methylcyclohexane.
• the solvents capable of dissolving the iron salt include alcohol solvents such as methanol, ethanol and isopropanol, and also tetrahydrofuran and the like.
• iron salts examples include iron (II) chloride, iron (III) chloride, iron (II) bromide, iron (III) bromide, iron (II) acetylacetonate, iron (III) acetylacetonate, iron (II) acetate and iron (III) acetate.
• these salts those having a ligand such as a solvent or water may be used.
• the salts of iron (II) are preferable and iron (II) chloride is more preferable.
• the solvents to which the diimine compound and the iron are brought into contact is not particularly limited, and both nonpolar and polar solvents can be used.
• the nonpolar solvents include hydrocarbon solvents such as hexane, heptane, octane, benzene, toluene, xylene, cyclohexane and methylcyclohexane.
• the polar solvents include polar protic solvents such as alcohol solvents and polar aprotic solvents such as tetrahydrofuran.
• the alcohol solvents include methanol, ethanol and isopropyl alcohol.
• a hydrocarbon solvent that does not substantially impact the olefin polymerization.
• the mixing ratio of the diimine compound and the iron when bringing them into contact is not particularly limited.
• the ratio of the diimine compound/iron may be, in molar ratio, 0.2/1 to 5/1, 0.3/1 to 3/1, 0.5/1 to 2/1, or 1/1.
• the two imine moieties of the diimine compound are both E-forms, but if a diimine compound with both E-forms is included, a diimine compound including a Z-form may be included. Since it is hard for a diimine compound including a Z-form to form a complex with a metal, it is possible to easily remove it by a purification step such as solvent washing after forming the complex in the system.
• the catalyst for the oligomerization contains trialkylaluminum besides the iron complex represented by the above Formula (1).
• the trialkylaluminum may be a trialkylaluminum having an alkyl group having 10 or less carbon atoms, or a trialkylaluminum having an alkyl group having 8 or less carbon atoms.
• examples of such trialkylaluminum include trimethylaluminum, triethylaluminum, triisobutylaluminum, tributylaluminum, trihexylaluminum and trioctylaluminum.
• the trialkylaluminum includes at least one selected from the group consisting of trimethylaluminum, triethylaluminum and triisobutylaluminum, and it is more preferable for the trialkylaluminum to include trimethylaluminum.
• the catalyst for the oligomerization can further contain optional components.
• the optional components include boron compounds and methylaluminoxane.
• Boron compounds function as a promoter which further improves the catalyst activity of the iron complex represented by the above Formula (1) in the olefin polymerization reaction.
• boron compounds examples include aryl boron compounds such as tris(pentafluorophenyl)borane.
• boron compounds having an anion species can be used.
• examples include aryl borates such as tetrakis(pentafluorophenyl)borate and tetrakis[3,5-(trifluoromethyl)phenyl]borate.
• aryl borates include lithium tetrakis(pentafluorophenyl)borate, sodium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, trityl tetrakis(pentafluorophenyl)borate, lithium tetrakis(3,5-trifluoromethylphenyl)borate, sodium tetrakis(3,5-trifluoromethylphenyl)borate, N,N-dimethylanilinium tetrakis(3,5-trifluoromethylphenyl)borate and trityl tetrakis(3,5-trifluoromethylphenyl)borate.
• N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, trityl tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(3,5-trifluoromethylphenyl)borate and, trityl tetrakis(3,5-trifluoromethylphenyl)borate are preferable.
• These boron compounds may be used singly or in combinations of two or more.
• methylaluminoxane the commercially available product diluted with a solvent can be used.
• modified methylaluminoxane obtained by modifying methylaluminoxane by an active proton compound such as phenol or its derivatives may be used.
• H the number of moles of trialkylaluminum
• Y as the number of moles of aluminum atoms in methylaluminoxane.
• the production method of the catalyst according to this embodiment is not particularly limited, and examples thereof include a method in which a solution containing trialkylaluminum is added to and mixed with a solution containing the iron complex represented by the above mentioned Formula (1), and a method in which a solution containing the iron complex represented by Formula (1) is added to and mixed with a solution containing trialkylaluminum.
• the iron complex represented by Formula (1), the trialkylaluminum and the optional components may be brought into contact all at once, or may be brought into contact in an arbitrary order.
• Examples of the production method of the catalyst when it contains optional components include a method in which a solution containing trialkylaluminum is added to and mixed with a solution containing the iron complex represented by Formula (1), and then the resultant is brought into contact with methylaluminoxane, a method in which a solution containing the iron complex represented by Formula (1) is brought into contact with the boron compound, and then a solution containing trialkylaluminum is added and mixed, and a method in which a solution containing the iron complex represented by Formula (1) is brought into contact with the boron compound, and then a solution containing trialkylaluminum is added and mixed, and the resultant is brought into contact with methylaluminoxane.
• the catalyst according to this embodiment may further contain the compound represented by the following Formula (2) (hereinafter also referred to as ligand), as needed.
• Formula (2) hereinafter also referred to as ligand
• R′′ represents a hydrocarbyl group having 1 to 6 carbon atoms or an aromatic group having 6 to 12 carbon atoms, a plurality of R′′ in the same molecule may be the same or different, R′′′ represents a free radical having an oxygen atom and/or a nitrogen atom, a plurality of R′′′ in the same molecule may be the same or different.
• the present inventors have confirmed that, in the step of oligomerizing the polymerizable monomer, when the oligomerization reaction progresses over a long time, the number average molecular weight (Mn) of the obtained polymer increases and the molecular weight distribution (Mw/Mn) sometimes tends to become wider. It is believed that this may be caused by a decrease in the original function of the iron complex represented by Formula (1), due to some structural change having occurred in the iron complex, including a break in the bond between the diimine compound and the iron in the iron complex as the oligomerization reaction progresses.
• the iron complex before the structural change is reproduced by re-binding of the ligand and the iron in the iron complex during the oligomerization reaction. Therefore, it is believed that, even if the reaction progresses over a long time, the increase in molecular weight of the obtained polymer may be suppressed.
• the present inventors have also confirmed that, since the iron salt such as iron chloride does not dissolve in the polymerization solvent such as toluene and does not form a complex, a similar effect cannot be obtained by just simply adding the ligand and the iron separately.
• hydrocarbyl group having 1 to 6 carbon atoms examples include alkyl groups having 1 to 6 carbon atoms and alkenyl groups having 2 to 6 carbon atoms.
• the hydrocarbyl group may be either linear, branched or cyclic.
• the hydrocarbyl group may also be a monovalent group in which a linear or branched hydrocarbyl group and a cyclic hydrocarbyl group are bonded.
• alkyl groups having 1 to 6 carbon atoms include linear alkyl groups having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a n-propyl group, a n-butyl group, a n-pentyl group and a n-hexyl group; branched alkyl groups having 3 to 6 carbon atoms such as an iso-propyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group, a branched pentyl group (including all structural isomers), and a branched hexyl group (including all structural isomers); and cyclic alkyl groups having 1 to 6 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
• alkenyl groups having 2 to 6 carbon atoms include linear alkenyl groups having 2 to 6 carbon atoms such as an ethenyl group (vinyl group), a n-propenyl group, a n-butenyl group, a n-pentenyl group, and a n-hexenyl group; branched alkenyl groups having 2 to 6 carbon atoms such as an iso-propenyl group, an iso-butenyl group, a sec-butenyl group, a tert-butenyl group, a branched pentenyl group (including all structural isomers), and a branched hexenyl group (including all structural isomers); and cyclic alkenyl groups having 2 to 6 carbon atoms such as a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, a cyclopentadienyl group
• aromatic groups having 6 to 12 carbon atoms include a phenyl group, a toluyl group, a xylyl group and a naphthyl group.
• a plurality of R′′ in the same molecule may be the same or different, but from a viewpoint of simplifying the synthesis of the compound, they may be the same.
• the free radical having an oxygen atom and/or a nitrogen atom may be a free radical having 0 to 6 carbon atoms and having an oxygen atom and/or a nitrogen atom, and examples thereof include a methoxy group, an ethoxy group, an isopropoxy group and a nitro group.
• Such ligand include the compounds represented by the following Formulas (2a) to (2d). These ligands may be used singly or in combinations of two or more.
• the R in Formula (1) and the R′′ in Formula (2), and the R′ in Formula (1) and the R′′′ in Formula (2) may respectively be the same or different, but from a viewpoint of maintaining a performance similar to that of the iron complex represented by Formula (1), it is preferable that they are the same.
• the compound represented by the above Formula (2) can be synthesized by a similar method as the method for the above mentioned diimine compound, and so a redundant description will be omitted here.
• the content ratio of the iron complex represented by the above Formula (1) and the ligand is not particularly limited.
• the lower limit of the ligand/iron complex ratio is, in molar ratio, preferably 1/100, more preferably 1/20, further preferably 1/10 and especially preferably 1/5.
• the upper limit of the ligand/iron complex ratio is, in molar ratio, preferably 100/1, more preferably 50/1, further preferably 10/1, especially preferably 5/1, highly preferably 3/1 and further highly preferably 1/1.
• the ligand/iron complex ratio is 1/100 or more, it allows to sufficiently exhibit the addition effect of the ligand, and if it is 100/1 or less, it allows to exhibit the addition effect of the ligand, while suppressing the costs. From such viewpoint, the ligand/iron complex ratio is, for example, 1/100 to 100/1, 1/20 to 50/1, 1/10 to 10/1, 1/5 to 5/1, or 1/5 to 1/1.
• the order of addition of the compound represented by the above Formula (2), when further contained, is not particularly limited, and examples thereof include a method in which a solution containing trialkylaluminum is added to and mixed with a solution containing the above described iron complex and the ligand, and a method in which a solution containing the ligand is added to and mixed with a solution containing the iron complex and trialkylaluminum.
• the ligand may be added after purifying the iron complex from the reaction mixture of the diimine compound and the iron salt obtained during the synthesis of the iron complex represented by Formula (1), but the diimine compound may also be left present in the catalyst as a ligand, without purifying the iron complex from the reaction mixture, that is, without removing the unreacted amine compound and iron salt.
• the production method of the oligomer in this embodiment includes a step of oligomerizing a polymerizable monomer comprising an olefin in the presence of the catalyst according to this embodiment described above.
• Examples of the olefins include ethylene and ⁇ -olefins.
• Examples of ⁇ -olefins include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, but also those having a branch of a methyl group etc. other than at position 2 such as 4-methyl-1-pentene.
• propylene may be used from a viewpoint of reactivity.
• the oligomer obtained by the production method according to this embodiment may be a homopolymer of one of the above olefins, or a copolymer of two or more of the above olefins.
• Such oligomer may be, for example, a homopolymer of ethylene, a homopolymer of propylene, or a copolymer of ethylene and propylene.
• the oligomer may further contain a structural unit derived from a monomer other than olefins.
• the polymerizable monomers used in this embodiment may consist of ethylene or an ⁇ -olefin, or they can further contain monomers other than ethylene or an ⁇ -olefin.
• an example of one aspect of the production method according to this embodiment is a method in which the polymerizable monomer is introduced in the reactor filled with the catalyst.
• the method for introducing the polymerizable monomers to the reactor is not particularly limited, but if the polymerizable monomer is a monomer mixture containing two or more olefins, the monomer mixture may be introduced in the reactor, or each polymerizable monomer may be introduced separately.
• a solvent may be used during the oligomerization.
• the solvents include aliphatic hydrocarbon solvents such as butane, pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane and decalin; and aromatic hydrocarbon solvents such as tetralin, benzene, toluene and xylene.
• the catalyst can be dissolved in these solvents and solution polymerization, slurry polymerization and the like can be performed.
• the reaction temperature of the oligomerization is not particularly limited, but from a viewpoint of further improving the catalyst efficiency, it may be, for example, ⁇ 50° C. to 100° C., ⁇ 30° C. to 80° C., ⁇ 20° C. to 70° C., 0° C. to 50° C., 5° C. to 30° C., or 5° C. to 15° C. If the reaction temperature is ⁇ 50° C. or more, the deposition of the oligomer generated can be suppressed while maintaining more sufficiently the catalyst activity, and if 100° C. or less, the decomposition of the catalyst can be suppressed.
• the reaction pressure is also not particularly limited, but may be, for example, 100 kPa to 5 MPa.
• the reaction time is also not particularly limited, but may be, for example, 1 minute to 24 hours, 5 minutes to 60 minutes, 10 minutes to 45 minutes, or 20 minutes to 40 minutes.
• oligomer means a polymer with a number average molecular weight (Mn) of 10000 or less.
• Mn number average molecular weight
• the Mn of the oligomer obtained by the production method of an oligomer according to this embodiment above can be adjusted appropriately according to the purpose of use.
• the Mn of the oligomer is preferably 200 to 5000, more preferably 300 to 4000, and further preferably 350 to 3000.
• the dispersion degree is a ratio of the weight-average molecular weight (Mw) to Mn and is expressed as Mw/Mn, but it may be, for example, 1.0 to 5.0 or 1.1 to 3.0.
• the Mn and Mw of the oligomers can be found, for example, in terms of polystyrene based on the calibration curve formed from standard polystyrene using a GPC device.
• the production method according to this embodiment is useful as a production method of base materials for lubricating oils such as olefin oligomer wax or poly- ⁇ -olefins (PAO).
• the oligomers obtained by the production method according to this embodiment can be preferably used as components of, for example, lubricating oil compositions.
• An iron complex was synthesized according to the method shown in the synthesis example described below.
• the reagents used were purchased articles as they were.
• For the trimethylaluminum a trimethylaluminum toluene solution produced by Tokyo Chemical Industry was used as is.
• For the triisobutylaluminum triisobutylaluminum produced by Nippon Aluminum Alkyls was used after being diluted with toluene. Trityl tetrakis(pentafluorophenyl)borate produced by Tokyo Chemical Industry was used as is.
• Bis(cyclopentadienyl)zirconium dichloride produced by Tokyo Chemical Industry was used as is.
• the catalyst efficiency was calculated by dividing the weight of the obtained oligomer by the number of moles of the catalyst used.
• the molecular sieve was removed from the reaction solution by filtration, and the molecular sieve was washed with toluene.
• the washing liquid and the filtered reaction solution was mixed, and the resultant was concentrated to dryness to obtain a crude solid (2.8241 g).
• the obtained crude solid (2 g) was weighed and washed with anhydrous ethanol (30 mL).
• the solid insoluble in ethanol was filtered off and this insoluble solid was further washed with ethanol.
• the residual solid was sufficiently dried to obtain the following diimine compound (I) with a yield of 50%.
• FeCl 2 .4H 2 O (0.2401 g, 1.2 mmol, produced by Kanto Chemical) was dissolved in dry tetrahydrofuran (30 mL, produced by Aldrich) and a tetrahydrofuran solution (10 mL) of the diimine compound (I) (0.4843 g, 1.2 mmol) was added. By adding the yellow diimine compound, it immediately became a dark green tetrahydrofuran solution. It was then further stirred for 2 hours at room temperature. The solvent was evaporated to dryness from the reaction solution. The resultant solid was continuously washed with dry ethanol until the filtrate became colorless.
• a 660 mL autoclave with an electromagnetic induction stirrer was sufficiently dried beforehand at 110° C. under reduced pressure. Next, under nitrogen, dry toluene (80 mL) was introduced in the autoclave, and the temperature was adjusted to 10° C.
• the iron complex obtained in Production Example 2 (1 ⁇ mol) was dissolved in 20 mL of dry toluene in a 50 mL flask and under nitrogen to form a solution (A).
• a 500 equivalent amount of trimethylaluminum (TMA) solution with respect to the iron complex was added to the solution (A) and the resultant was stirred for 5 minutes to obtain a solution (B) containing the catalyst.
• the solution (B) was added to the autoclave where dry toluene was introduced, and ethylene at 0.19 MPa was introduced continuously at 10° C. The introduction of ethylene was stopped after 30 minutes, the unreacted ethylene was removed, the ethylene in the autoclave was purged with nitrogen, and a very small amount of ethanol was added.
• the autoclave was opened, the content was transferred to a 200 mL flask and the solvent was distilled off under reduced pressure to obtain a semi-solid oligomer.
• the catalyst efficiency (C.E.) was 1479 Poly/Fe mol.
• the Mn of the obtained oligomer was 550 and Mw/Mn was 1.6.
• Example 2 Besides setting the temperature of the autoclave to room temperature (25° C.) when continuously introducing ethylene, the same operations as in Example 1 were performed.
• the catalyst efficiency (C.E.) was 1398 kg Poly/Fe mol.
• the Mn of the obtained oligomer was 370 and Mw/Mn was 1.3.
• the iron complex obtained in Production Example 2 (1 ⁇ mop and trityl tetrakis(pentafluorophenyl)borate (1 ⁇ mop was dissolved in 20 mL of dry toluene in a 50 mL flask and under nitrogen to form a solution (A).
• a 500 equivalent amount of TMA solution with respect to the iron complex was added to the solution (A) and the resultant was stirred for 5 minutes to obtain a solution (B) containing the catalyst.
• the solution (B) was added to the autoclave where dry toluene was introduced, and ethylene at 0.19 MPa was introduced continuously at 10° C.
• the introduction of ethylene was stopped after 30 minutes, the unreacted ethylene was removed, the ethylene in the autoclave was purged with nitrogen, and a very small amount of ethanol was added.
• the autoclave was opened, the content was transferred to a 200 mL flask and the solvent was distilled off under reduced pressure to obtain a semi-solid oligomer.
• the catalyst efficiency (C.E.) was 3276 kg Poly/Fe mol.
• the Mn of the obtained oligomer was 500 and Mw/Mn was 1.6.
• Example 3 Besides adding a 100 equivalent amount of TMA solution with respect to the iron complex in the preparation step of solution (B), the same operations as in Example 3 were performed.
• the catalyst efficiency (C.E.) was 6455 kg Poly/Fe mol.
• the Mn of the obtained oligomer was 460 and Mw/Mn was 1.6.
• the iron complex obtained in Production Example 2 (1 ⁇ mol) was dissolved in 20 mL of dry toluene in a 50 mL flask and under nitrogen to form a solution (A).
• a 500 equivalent amount of TMA solution with respect to the iron complex was added to the solution (A), further a 500 equivalent amount based on an aluminum atom of methylaluminoxane (MAO) with respect was added to the iron complex and the resultant was stirred for 5 minutes to obtain a solution (B) containing the catalyst.
• the solution (B) was added to the autoclave where dry toluene was introduced, and ethylene at 0.19 MPa was introduced continuously at 40° C.
• the introduction of ethylene was stopped after 30 minutes, the unreacted ethylene was removed, the ethylene in the autoclave was purged with nitrogen, and a very small amount of ethanol was added.
• the autoclave was opened, the content was transferred to a 200 mL flask and the solvent was distilled off under reduced pressure to obtain a semi-solid oligomer.
• the catalyst efficiency (C.E.) was 4908 kg Poly/Fe mol.
• the Mn of the obtained oligomer was 420 and Mw/Mn was 1.5.
• Example 4 Besides adding a 100 equivalent amount of triisobutylaluminum (TIBA) solution with respect to the iron complex instead of a TMA solution in the preparation step of solution (B), and also setting the temperature of the autoclave to room temperature (25° C.) when continuously introducing ethylene, the same operations as in Example 4 were performed.
• the catalyst efficiency (C.E.) was 482 kg Poly/Fe mol.
• the Mn of the obtained oligomer was 540 and Mw/Mn was 1.4.
• a 20 L autoclave with an electromagnetic induction stirrer was sufficiently dried beforehand at 110° C. under reduced pressure. Next, under nitrogen, dry toluene (7.6 L) was introduced in the autoclave, and the temperature was adjusted to 0° C.
• the iron complex obtained in Production Example 2 (42.2 mg) and 1 equivalent amount of trityl tetrakis(pentafluorophenyl)borate with respect to the iron complex (73.8 mg) was dissolved in 200 ml, of dry toluene in a 500 mL flask and under nitrogen to form a solution (A).
• a 100 equivalent amount of trimethylaluminum (TMA) solution with respect to the iron complex was added to the solution (A) and the resultant was stirred for 5 minutes to obtain a solution (B) containing the catalyst.
• TMA trimethylaluminum
• a solution (C) was obtained by further adding the diimine compound (I) obtained in Production Example 1 in 0.33 equivalent amount with respect to the iron complex, to the solution (B) as a ligand (compound 2(a)).
• This solution (C) was added to the above autoclave where dry toluene was introduced and ethylene at 0.2 MPa was introduced continuously at 0° C. The introduction of ethylene was stopped after 970 minutes, the unreacted ethylene was removed, the ethylene in the autoclave was purged with nitrogen, and a very small amount of ethanol was added. The autoclave was opened, sequentially the content was transferred to a 20 L evaporator and the solvent was distilled off the solvent under reduced pressure to obtain a semi-solid oligomer.
• the catalyst efficiency (C.E.) was 68875 Poly/Fe mol.
• the Mn of the obtained oligomer was 550 and Mw/Mn was 1.7.
• Example 7 Besides not further adding a ligand to the solution (B) and setting the reaction time to 920 min, the same operations as in Example 7 were performed.
• the catalyst efficiency (C.E.) was 57838 kg Poly/Fe mol.
• the Mn of the obtained oligomer was 530 and Mw/Mn was 1.6.
• a 660 mL autoclave with an electromagnetic induction stirrer was sufficiently dried beforehand at 110° C. under reduced pressure. Next, under nitrogen, dry toluene (80 mL) was introduced in the autoclave, and the temperature was adjusted to 10° C.
• the iron complex obtained in Production Example 2 (1 ⁇ mop and trityl tetrakis(pentafluorophenyl)borate (1 mol), and as the ligand (compound 2(a)), the diimine compound (I) obtained in Production Example 1 in 0.5 equivalent amount with respect to the iron complex were dissolved in 20 mL of dry toluene in a 50 mL flask and under nitrogen to form a solution (A).
• a 100 equivalent amount of trimethylaluminum (TMA) solution with respect to the iron complex was added to the solution (A) and the resultant was stirred for 5 minutes to obtain a solution (B) containing the catalyst.
• TMA trimethylaluminum
• the solution (B) was added to the autoclave where dry toluene was introduced, and ethylene at 0.19 MPa was introduced continuously at 10° C. The introduction of ethylene was stopped after 60 minutes, the unreacted ethylene was removed, the ethylene in the autoclave was purged with nitrogen, and a very small amount of ethanol was added. The autoclave was opened, the content was transferred to a 200 mL flask and the solvent was distilled off under reduced pressure to obtain a semi-solid oligomer.
• the catalyst efficiency (C.E.) was 8215 Poly/Fe mol.
• the Mn of the obtained oligomer was 340 and Mw/Mn was 2.2.
• a 660 mL autoclave with an electromagnetic induction stirrer was sufficiently dried beforehand at 110° C. under reduced pressure. Next, under nitrogen, dry toluene (80 mL) was introduced in the autoclave, and the temperature was adjusted to 10° C.
• the iron complex obtained in Production Example 2 (1 ⁇ mol) and trityl tetrakis(pentafluorophenyl)borate (1 ⁇ mop was dissolved in 20 mL of dry toluene in a 50 mL flask and under nitrogen to form a solution (A).
• a 100 equivalent amount of trimethylaluminum (TMA) solution with respect to the iron complex was added to the solution (A) and the resultant was stirred for 5 minutes to obtain a solution (B) containing the catalyst.
• a solution (C) containing the catalyst was obtained by adding the diimine compound (I) obtained in Production Example 1 in 0.5 equivalent amount with respect to the iron complex, to the solution (B) as the ligand (compound 2(a)).
• the solution (C) was added to the autoclave where dry toluene was introduced, and ethylene at 0.19 MPa was introduced continuously at 10° C. The introduction of ethylene was stopped after 60 min, the unreacted ethylene was removed, the ethylene in the autoclave was purged with nitrogen, and a very small amount of ethanol was added. The autoclave was opened, the content was transferred to a 200 mL flask and the solvent was distilled off under reduced pressure to obtain a semi-solid oligomer.
• the catalyst efficiency (C.E.) was 10524 Poly/Fe mol.
• the Mn of the obtained oligomer was 300 and Mw/Mn was 2.2.

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